CN110467731B - Preparation method of stable ultrathin mesoporous metal organic framework material - Google Patents
Preparation method of stable ultrathin mesoporous metal organic framework material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 66
- 239000013337 mesoporous metal-organic framework Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 63
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 45
- 239000011259 mixed solution Substances 0.000 claims abstract description 34
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007767 bonding agent Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 24
- 239000013110 organic ligand Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical class [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Chemical class 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Chemical class 0.000 claims description 2
- 239000010955 niobium Chemical class 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical class [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical class [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Chemical class 0.000 claims description 2
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical class [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000000725 suspension Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 239000002135 nanosheet Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- 239000001301 oxygen Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 238000003917 TEM image Methods 0.000 description 3
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- 229920000557 Nafion® Polymers 0.000 description 2
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- 229910009045 WCl2 Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910015224 MoCl2 Inorganic materials 0.000 description 1
- 229910021549 Vanadium(II) chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal chalcogenides Chemical class 0.000 description 1
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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Abstract
The invention relates to a preparation method of a stable mesoporous metal organic framework material, which adopts a two-step method: firstly ultrasonic and then hydrothermal or solvent heat treatment. Respectively placing N, N-dimethylformamide, ethanol and water in a liner of a reaction kettle, then ultrasonically dispersing terephthalic acid in the mixed solution, adding different combinations of divalent metal salts, stirring to uniformly disperse the divalent metal salts, and then adding triethylamine as an acid bonding agent. Firstly, ultrasonic reaction is carried out for a certain time, and then the mixture is transferred to a high-pressure reaction kettle for continuous reaction. And cooling to room temperature, and centrifugally washing and drying to obtain the ultrathin metal organic framework material. The ultrathin metal organic framework material prepared by the invention has a continuous mesoporous structure, and the catalytic activity is improved.
Description
Technical Field
The invention relates to a preparation method of a stable ultrathin mesoporous metal organic framework material. The ultrathin metal organic framework nanosheet obtained by the method has a continuous mesoporous structure, is simple and easy to prepare, and is mainly used for catalytic materials, adsorption materials, energy storage materials and the like.
Background
In recent years, two-dimensional materials represented by graphene and transition metal chalcogenides have received much attention from the scientific community and the industrial community. Due to the ultrathin thickness (usually several atomic layers thick) and the sheet structure, the nano materials show many unique properties and have huge application prospects in the fields of energy sources, devices and the like. Metal Organic Frameworks (MOFs) are porous periodic network framework materials formed by self-assembly of Metal ion/atom clusters and Organic ligands (mainly carboxyl-containing Organic anion ligands) through coordination, and are novel porous materials which have attracted attention in recent years. Due to the good structural characteristics, the catalyst is widely applied to the fields of gas storage and separation, catalysis, sensing and the like.
In this context, two-dimensional MOFs are an important material with a wide range of applications. However, MOF materials have been reported to be mostly restricted to microporous structures, with small pore sizes hindering mass transfer movements and preventing contact of larger guest molecules with the internal active sites of MOFs. Therefore, it is necessary to prepare MOF materials with a layered structure, larger interconnected pores.
In order to enlarge the pore size, it has been reported that a template method for preparing MOF materials can obtain ordered/disordered pore structures after removing the template, and such a method has the advantage that the MOF pores can be controlled by adjusting the template structure, but the pore structures of MOF may collapse when removing the template, and the control process of sacrificing the template is complicated, so that a template-free preparation method is urgently needed to avoid the above problems.
Disclosure of Invention
The invention aims to disclose a method for synthesizing a stable ultrathin mesoporous metal organic framework material, which is a technology for synthesizing porous MOF with a multi-stage structure by a template-free method for the first time.
In order to achieve the aim, the method adopts an ultrasonic-hydrothermal or solvothermal two-step method, and the two-dimensional MOF after ultrasonic treatment removes unstable MOF structures in the hydrothermal or solvothermal process so as to generate continuous mesopores, and enhances the active sites of the MOF, thereby improving the catalytic activity, the adsorption capacity and the energy storage capacity of the MOF.
The specific process comprises the following steps:
(1) measuring N, N-dimethylformamide, ethanol and water according to a certain volume part, placing the mixture into a liner of a reaction kettle, and then adding an organic ligand to ultrasonically disperse the mixture in a mixed solution;
(2) adding divalent metal salt into the mixed solution obtained in the step (1), and stirring to uniformly disperse the divalent metal salt;
(3) adding triethylamine serving as an acid bonding agent into the mixed solution obtained in the step (2), stirring to uniformly disperse the mixed solution, and then reacting for a certain time in an ultrasonic environment;
(4) transferring the product obtained by the ultrasonic treatment in the step (3) to a high-pressure reaction kettle, and carrying out hydrothermal or solvent heat treatment;
(5) and (4) cooling the product obtained in the step (4) after the hydrothermal treatment to room temperature, centrifugally washing, and drying to obtain the more stable ultrathin metal organic framework material.
Further, the volume ratio of the N, N-dimethylformamide to the ethanol to the water in the mixed solution in the step (1) is 8: 0-4: 0 to 4. The organic ligand is terephthalic acid; the molar volume ratio of the organic ligand to the mixed solution is 0.01-0.04 mmol/ml.
Further, the divalent metal salt in the step (2) comprises one or two or more of metal salts of iron, cobalt, nickel, molybdenum, vanadium, tungsten and niobium.
Further, the reaction time in the ultrasonic environment in the step (3) is 1-12 hours, and 0-5% of triethylamine is added into the mixed solution before ultrasonic treatment to serve as an acid bonding agent.
Further, the hydrothermal or solvent heat treatment temperature in the step (4) is 100-260 ℃ and the time is 8-50 hours.
Furthermore, the metal organic framework material has an obvious mesoporous structure of 2-10 nanometers.
The stable ultrathin mesoporous metal organic framework material prepared by the method is used for carrying out adsorption performance test, energy storage capacity test or electrochemical performance test. For example, the electrochemical performance test procedure is as follows: the obtained MOF material, ethanol, water and perfluorosulfonic acid-polytetrafluoroethylene copolymer (Nafion) are mixed and then dripped on a glassy carbon electrode to be used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a graphite electrode is used as a counter electrode, and an electrolyte is a prepared standard KOH solution with the concentration of 1 mol/L. During the test, the scanning interval of the voltage is 0.0-0.8V, the scanning speed is 5mV/s, and the activity test of oxygen evolution by electrolyzed water is carried out.
The invention has the advantages that:
(1) the invention provides a more stable preparation method of an ultrathin mesoporous metal organic framework material. The invention adopts a template-free method to prepare the layered porous metal organic framework material for the first time. Compared with the prior template method, the method has simple and easy control process, and can also avoid the damage to the MOF pore structure when the template is removed.
(2) Currently, the synthesized MOF material is basically only provided with micropores and has larger thickness. Compared with the two methods, the metal organic framework material prepared by the two-step method has an ultrathin sheet structure (the thickness of a single layer sheet is less than 2nm), and meanwhile, the ultrathin nanosheet also has a continuous mesoporous structure (the average pore diameter is less than 10 nm).
(3) The ultrathin mesoporous metal organic framework material prepared by the invention has a large number of active sites, is beneficial to the contact of substrate molecules and the active sites, and can further improve the performances of MOF in the fields of catalysis, sensing, energy storage, adsorption and the like. In the test process of oxygen evolution reaction, the current density of the MOF nanosheet prepared by adopting a two-step method is 10 mA-cm-2The time overpotential is only 277mV, and the Tafel slope is 31mV dec-1(the overpotential of the material prepared by only adopting an ultrasonic method is 300mV, and the Tafel slope is 40mV dec-1(ii) a The material prepared by only adopting a hydrothermal method has the overpotential of 310mV and the Tafel slope of 56mV dec-1) The structural advantages are proved.
Drawings
FIG. 1 is a transmission electron micrograph of a MOF obtained in example 1 of the present invention. From this figure, it can be seen that the MOF material produced is a nanosheet with mesopores.
FIG. 2 shows CoFe-MOF material and commercial RuO obtained in example 1 of the present invention2Linear sweep voltammetry curve contrast plot for oxygen evolution reaction. As can be seen from FIG. 2, the obtained CoFe-MOF material has better performance.
FIG. 3 is a transmission electron micrograph of a NiV-MOF material obtained in example 3 of the present invention. From FIG. 3, it can be seen that the NiV-MOF material prepared is a nanosheet having mesopores.
FIG. 4 is a transmission electron micrograph of a Ni-MOF material obtained in example 4 of the present invention. From FIG. 4, it can be seen that the prepared Ni-MOF material is a nanosheet having mesopores.
Detailed Description
The invention will be described in more detail with reference to the following figures and examples, but the scope of the invention is not limited thereto.
Example 1: a preparation method of an ultrathin mesoporous metal organic framework material comprises the following specific steps:
(1) 32mL of N, N-Dimethylformamide (DMF), 2mL of ethanol and 2mL of deionized water were added to the reactor liner. 0.75mmol of terephthalic acid (BDC) is added into the mixed solution and dispersed evenly.
(2) To the above solution was added 0.375mmol of CoCl2.6H2O and 0.375mmol FeCl2.4H2And O, after the dispersion is uniform, quickly adding 0.8mL of Triethylamine (TEA) serving as a bonding agent of the metal ions and the organic ligand, stirring to form uniform colloidal suspension, and carrying out ultrasonic treatment for 8 hours.
(3) Transferring the mixed solution obtained after the ultrasonic treatment to a high-pressure reaction kettle, and reacting for 48 hours at 140 ℃.
(4) And cooling the obtained product to room temperature, centrifugally washing, and drying to obtain the ultrathin lamellar mesoporous CoFe-MOF material.
And (3) electrochemical performance testing: performing ultrasonic treatment on 5mg of CoFe-MOF, 0.8mL of water, 0.2mL of ethanol and 50 muL of 5% perfluorosulfonic acid-polytetrafluoroethylene copolymer (Nafion) for 30min, dripping the mixture on a glassy carbon electrode, and drying for 20min to obtain a working electrode; the Ag/AgCl electrode is used as a reference electrode, the graphite electrode is used as a counter electrode, and the electrolyte is a prepared standard KOH solution with the concentration of 1 mol/L. During the test, the scanning interval of the voltage is 0.0-0.8V, the scanning speed is 5mV/s, and the activity test of oxygen evolution by electrolyzed water is carried out.
The transmission electron microscope picture of the CoFe-MOF material prepared in this example is shown in FIG. 1, and it can be seen from FIG. 1 that the material has a nano-sheet structure with mesopores. The comparison of linear sweep voltammetry curves of the oxygen evolution reaction of the CoFe-MOF material prepared by the embodiment is shown in FIG. 2, which shows that the catalytic activity of the ultrathin mesoporous CoFe-MOF material prepared by the method is obviously improved and can be compared with commercial RuO2The catalytic activity is higher.
Example 2: a preparation method of an ultrathin mesoporous metal organic framework material comprises the following specific steps:
(1) 32mL of N, N-Dimethylformamide (DMF), 0.5mL of ethanol and 0.5mL of deionized water were added to the reactor liner. 0.33mmol of terephthalic acid (BDC) is added into the mixed solution and dispersed evenly.
(2) To the above solution was added 0.165mmol NiCl2.6H2O and 0.165mmol FeSO4.7H2And O, after the dispersion is uniform, quickly adding 0.35mL of Triethylamine (TEA) serving as a bonding agent of metal ions and organic ligands, stirring to form uniform colloidal suspension, and carrying out ultrasonic treatment for 1 h.
(3) Transferring the mixed solution obtained after the ultrasonic treatment to a high-pressure reaction kettle, and reacting for 10 hours at 260 ℃.
(4) And cooling the obtained product to room temperature, centrifugally washing, and drying to obtain the ultrathin layer mesoporous NiFe-MOF material.
Example 3: a preparation method of an ultrathin mesoporous metal organic framework material comprises the following specific steps:
(1) 32mL of N, N-Dimethylformamide (DMF), 2mL of ethanol and 2mL of deionized water were added to the reactor liner. 0.75mmol of terephthalic acid (BDC) is added into the mixed solution and dispersed evenly.
(2) To the solution was added 0.375mmol NiCl2.6H2O and 0.375mmol VCl2After the dispersion is uniform, 0.8mL of Triethylamine (TEA) is rapidly added as a bonding agent of metal ions and organic ligands, the mixture is stirred to form uniform colloidal suspension, and the colloidal suspension is subjected to ultrasonic treatment for 8 hours.
(3) Transferring the mixed solution obtained after the ultrasonic treatment to a high-pressure reaction kettle, and reacting for 48 hours at 140 ℃.
(4) And cooling the obtained product to room temperature, centrifugally washing, and drying to obtain the ultrathin layer mesoporous NiV-MOF material.
The transmission electron microscope picture of the NiV-MOF material prepared in this example is shown in fig. 3, and it can be seen from fig. 3 that the material has a nano-sheet structure with mesopores.
Example 4: a preparation method of an ultrathin mesoporous metal organic framework material comprises the following specific steps:
(1) 32mL of N, N-Dimethylformamide (DMF), 2mL of ethanol and 2mL of deionized water were added to the reactor liner. 0.75mmol of terephthalic acid (BDC) is added into the mixed solution and dispersed evenly.
(2) To the solution was added 0.75mmol NiCl2.6H2And O, after the dispersion is uniform, quickly adding 0.8mL of Triethylamine (TEA) serving as a bonding agent of the metal ions and the organic ligand, stirring to form uniform colloidal suspension, and carrying out ultrasonic treatment for 8 hours.
(3) Transferring the mixed solution obtained after the ultrasonic treatment to a high-pressure reaction kettle, and reacting for 48 hours at 140 ℃.
(4) And cooling the obtained product to room temperature, centrifugally washing, and drying to obtain the ultrathin sheet layer mesoporous Ni-MOF material.
The transmission electron microscope picture of the Ni-MOF material prepared in this example is shown in fig. 4, and it can be seen from fig. 4 that the material has a nano-sheet structure with mesopores.
Example 5: a preparation method of an ultrathin mesoporous metal organic framework material comprises the following specific steps:
(1) 32mL of N, N-Dimethylformamide (DMF), 2mL of ethanol and 2mL of deionized water were added to the reactor liner. 0.75mmol of terephthalic acid (BDC) is added into the mixed solution and dispersed evenly.
(2) To the solution was added 0.25mmol NiCl2.6H2O,0.25mmol CoCl2.6H2O and 0.25mmol FeCl2.4H2And O, after the dispersion is uniform, quickly adding 0.8mL of Triethylamine (TEA) serving as a bonding agent of the metal ions and the organic ligand, stirring to form uniform colloidal suspension, and carrying out ultrasonic treatment for 8 hours.
(3) Transferring the mixed solution obtained after the ultrasonic treatment to a high-pressure reaction kettle, and reacting for 48 hours at 140 ℃.
(4) And cooling the obtained product to room temperature, centrifugally washing, and drying to obtain the ultrathin lamellar mesoporous NiCoFe-MOF material.
Example 6: a preparation method of an ultrathin mesoporous metal organic framework material comprises the following specific steps:
(1) 32mL of N, N-Dimethylformamide (DMF) and 16mL of ethanol were added to the inner liner of the reaction vessel. 1.92mmol of terephthalic acid (BDC) was added to the above mixed solution and uniformly dispersed.
(2) To the solutionTo which 0.64mmol of NiCl was added2.6H2O,0.64mmol CoCl2.6H2O and 0.64mmol WCl2After dispersing evenly, the mixture is subjected to ultrasonic treatment for 5 hours.
(3) Transferring the mixed solution obtained after the ultrasonic treatment into a high-pressure reaction kettle, and reacting for 50 hours at 100 ℃.
(4) And cooling the obtained product to room temperature, centrifugally washing, and drying to obtain the ultrathin lamellar mesoporous NiCoW-MOF material.
Example 7: a preparation method of an ultrathin mesoporous metal organic framework material comprises the following specific steps:
(1) 32mL of N, N-Dimethylformamide (DMF) and 16mL of deionized water were added to the reactor liner. 1.92mmol of terephthalic acid (BDC) was added to the above mixed solution and uniformly dispersed.
(2) To the solution was added 0.64mmol NiCl2.6H2O,0.64mmol CoCl2.6H2O and 0.64mmol WCl2After the dispersion is uniform, 2.4mL of Triethylamine (TEA) is rapidly added as a bonding agent of metal ions and organic ligands, the mixture is stirred to form uniform colloidal suspension, and the colloidal suspension is subjected to ultrasonic treatment for 12 hours.
(3) Transferring the mixed solution obtained after the ultrasonic treatment to a high-pressure reaction kettle, and reacting for 50 hours at 130 ℃.
(4) And cooling the obtained product to room temperature, centrifugally washing, and drying to obtain the ultrathin lamellar mesoporous NiCoW-MOF material.
Example 8: a preparation method of an ultrathin mesoporous metal organic framework material comprises the following specific steps:
(1) 32mL of N, N-Dimethylformamide (DMF), 4mL of ethanol and 4mL of deionized water were added to the inner liner of the reaction vessel. 1.2mmol of terephthalic acid (BDC) is added into the mixed solution and dispersed evenly.
(2) To the solution was added 0.4mmol NiCl2.6H2O,0.4mmol CoCl2.6H2O,0.4mmol MoCl2After the dispersion is uniform, 01.28mL of Triethylamine (TEA) is rapidly added as a bonding agent of metal ions and organic ligands, the mixture is stirred to form a uniform colloidal suspension, and the colloidal suspension is subjected to ultrasonic treatment for 10 hours.
(3) Transferring the mixed solution obtained after the ultrasonic treatment into a high-pressure reaction kettle, and reacting for 40 hours at 150 ℃.
(4) And cooling the obtained product to room temperature, centrifugally washing, and drying to obtain the ultrathin lamellar mesoporous NiCoMo-MOF material.
Example 9: a preparation method of an ultrathin mesoporous metal organic framework material comprises the following specific steps:
(1) 36mL of N, N-Dimethylformamide (DMF), 1.8mL of ethanol, and 1.8mL of deionized water were added to the reactor liner. 0.81mmol of terephthalic acid (BDC) is added into the mixed solution and dispersed evenly.
(2) To the solution was added 0.27mmol NiCl2.6H2O,0.27mmol CoCl2.6H2O,0.27mmol NbCl2After the dispersion is uniform, 0.7mL of Triethylamine (TEA) is rapidly added as a bonding agent of metal ions and organic ligands, the mixture is stirred to form uniform colloidal suspension, and the colloidal suspension is subjected to ultrasonic treatment for 7 hours.
(3) Transferring the mixed solution obtained after the ultrasonic treatment to a high-pressure reaction kettle, and reacting for 45 hours at 130 ℃.
(4) And cooling the obtained product to room temperature, centrifugally washing, and drying to obtain the ultrathin lamellar mesoporous NiCoNb-MOF material.
Claims (4)
1. A preparation method of a stable ultrathin mesoporous metal organic framework material is characterized by comprising the following steps:
(1) measuring N, N-dimethylformamide, ethanol and water according to a certain volume part, placing the mixture into a liner of a reaction kettle, and then adding an organic ligand to ultrasonically disperse the mixture in a mixed solution;
(2) adding divalent metal salt into the mixed solution obtained in the step (1), and stirring to uniformly disperse the divalent metal salt;
(3) adding triethylamine serving as an acid bonding agent into the mixed solution obtained in the step (2), stirring to uniformly disperse the mixed solution, and then reacting for a certain time in an ultrasonic environment;
(4) transferring the product obtained by the ultrasonic treatment in the step (3) to a high-pressure reaction kettle for hydrothermal or solvothermal reaction;
(5) cooling the product obtained in the step (4) after hydrothermal treatment to room temperature, centrifugally washing, and drying to obtain the ultrathin metal organic framework material;
the metal organic framework material has an obvious mesoporous structure of 2-10 nanometers, and the thickness of a single layer of the metal organic framework material is less than 2 nm;
the divalent metal salt in the step (2) comprises one or two or more of metal salts of iron, cobalt, nickel, molybdenum, vanadium, tungsten and niobium.
2. The method for preparing the ultra-thin mesoporous metal organic framework material according to claim 1, wherein the method comprises the following steps: the volume ratio of the N, N-dimethylformamide to the ethanol to the water in the mixed solution in the step (1) is 8: 0-4: 0 to 4; the organic ligand is terephthalic acid; the molar volume ratio of the organic ligand to the mixed solution is 0.01-0.04 mmol/ml.
3. The method for preparing the ultra-thin mesoporous metal organic framework material according to claim 1, wherein the method comprises the following steps: and (4) reacting for 1-12 hours in the ultrasonic environment in the step (3), and adding triethylamine which is 0-5% of the volume of the mixed solution into the mixed solution before ultrasonic treatment to serve as an acid bonding agent.
4. The method for preparing the ultra-thin mesoporous metal organic framework material according to claim 1, wherein the method comprises the following steps: the treatment mode in the step (4) is hydrothermal or solvent thermal treatment in the reaction kettle, the temperature is 100 ℃ and 260 ℃, and the time is 8-50 hours.
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